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Analysis of organic electrode reactions by a thin layer electrochemical Raman method

薄层电化学拉曼法分析有机电极反应

基本信息

批准号：
09640724
负责人：
MORISHITA Fujio
金额：
$ 1.98万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

In this project, at first, we analyzed the reduction processes of chioranil in the presence of metal cations by developing a thin layer electrochemical resonance Raman method. Consequently, the differences in the reactions between in the homogeneous solutions and on the electrode surface have become clear. Also, the difference depending on the sort of metal cations has analyzed.In addition, we studied the electrochemical reduction process of tetracyanoquinodimethane (TCNQ) with the presence of the alkaline earth metal ion. Cyclic voltammogram of TCNQ reduction process with the presence of barium ion and magnesium ion in acetonitrile showed that the reduction process forming radical anion has no effect of the presence the metal ion, but the reduction process forming dianion has large effect of the metal ion. And in the oxidation scan, two oxidation peaks were observed which were attributed to desorption of adsorption deposits. From the EQCM measurement, it was appeared that the unit one metal ion with two radical anions grows on the electrode surface. And we could submit the structural growth model where radical anion dimer produced containing metal ion with the key step that forming TCNQ dianion. Therefore, to confirm the formation of dianion which is key step of the structural growth, we analyzed the deposit with using resonance Raman measurement. In the excitation using 514.5 nm laser, oxidant of TCNQ dianion was observed from the resonance Raman spectra, so the submitted model was confirmed. And also, in the excitation of 785 nm laser, TCNQ radical anion which was major product was observed.

在这个项目中，我们首先通过开发一种薄层电化学共振拉曼方法，分析了在金属阳离子存在下，氯氰胺的还原过程。因此，在均匀溶液中和在电极表面上的反应之间的差异已经变得清楚。此外，还分析了不同金属阳离子种类的差异。此外，我们还研究了碱土金属离子存在下四氰喹诺二甲烷（TCNQ）的电化学还原过程。在乙腈中存在钡离子和镁离子时的TCNQ还原过程的循环伏安图表明，形成自由基阴离子的还原过程对金属离子的存在没有影响，而形成阴离子的还原过程对金属离子的存在有较大的影响。在氧化扫描中，观察到两个氧化峰，这是由于吸附沉积物的解吸。从EQCM测量中可以看出，在电极表面生长的是带有两个自由基阴离子的单位一金属离子。提出了以形成TCNQ离子为关键步骤生成含金属离子的自由基阴离子二聚体的结构生长模型。因此，为了确定离子的形成是结构生长的关键步骤，我们使用了共振拉曼测量对矿床进行了分析。在514.5 nm激光激发下，从共振拉曼光谱中观察到TCNQ离子的氧化剂，从而证实了所提交的模型。在785 nm激光激发下，主要产物为TCNQ自由基阴离子。